Method of preparing alpha catalyst



May 334- N. E. oGLEs/BY Er An. A ,956,585

METHOD OF PREPARING' CTALYST /7 Filed Jan. l?, 1929 y v f re 22a? am@ M y M Zier-.s

NCYUZaS EZesy INVENTORS. Howard VVV/*ight A TTORNEYSl Patented May 1, 1934 i,5fi,585

1,956,585` METHOD or PREPARING A oA'rALYs'r Nicholas E. Oglesby and Howard V. Wright, Edge--l wood, Md.; said Oglesby assignor to said Wright Application January 17, 1929, serial No. 333,194 17 Claims. (Cl. 23-233) (Granted under the act of March 3, 1883, as amended April 30, 1928; 370 0. G. 757) This invention described herein may be manubon, there is a considerable evolution of heat, `factured and used by or for the Government for making the reaction quite difficult to control. government purposes, without the payment to us In ordilto make the preparation of catalysts of any royalty thereon economic y successful it is important to re- 5 This invention relates to catalysis and more cover for further use the valuable materials used particularly to a method of preparing certain 1n thte prczeslsl. In the (lass of the nitrato method metals and metallic oxides, such as copper, men ione is means he recovery of the oxides nickel, cobalt, zinc, and similar metals anld tthei'r Ottritzrogeyivvolved ir tle decfmpositlon of the oxides, in a form suitable for use as ca a ys s. n1 ra e. en a ni ra e is ecomposed with l It is common practice, when using metals sind llit Ith nitiigfen is egfolved as a mixture of NO2, 65y metallic oxides as catalytic agents, to emp oy 2 an ree ni rogen, Only the NO2 and some porous material as a carrier of the catalyst. the NO can be readily recovered for further use, The purpose of the material used as a carrier is vand the N20 and free nitrogen are usually lost. to support the finely divided catalyst in such a In heating activated carbon impregnated withl l5 way as to allow intimate contact between it and Copper nitrate this loss amounts to between 30 the materials entering into the reactionl;1 Singe antd +i0% oil .the nitrogen ptreent in trllle copper the value of a catalyst in many cases epen s n1 raue an is an impe an 1 am in e Cos of largely upon the amount of surface exposed to the catalyst. The recovery of NO2 and NO necesr2 the reacting materials, it is desirable to have StateS the 11S@ 0f acid resisting' equipment. fils@ the catalyst in as finely divided a state as posthe oxidation of the NO present in the mixture i75- sible. This condition is usually obtained by imtc N02 and the absorption of NO2 in water te pregnating the carrier with a water solution of form nitric acid involve a number of operating a suitable salt of the metal and then decomposand mechanical' diculties which decrease still ing the salt, usually by heat. This treatment further the economy of recovery of nitrogen, or

yields a catalyst either inthe form of the metal nitrogen compounds, ao or an oxide of the metal which, if desired, can It can readily be seen that the diiiiculties conthen be reduced to the metallic state. nected with the use of nitrates in preparing This method of preparation, while yielding a r'iktallic catalllyslts 1 i;'lake tlhe pricests at costly one. somewhat satisfactory product for use in catale use o s p a sin p ace o ni ra es hasbeen ysis, is subject to certain disadvantages. The attempted in order to reducethe cost o-` the 35 salts usually employed in the above process are catalyst. Sulphates are less costly than nitrates,

the sulfate and the nitrate. A relatively high and, because of the-low cost `of HzSOi, it is usually temperature is required to decompose both of considered cheaper to use fresh acid than to these salts, which is a material portion of the attempt the recovery of the S03 and SO2 evolved cost of the catalyst. The use of high temperain deciompoing the llulphat.. E Iiwever, sulphur eo tures also results, with some metals, in a de- 10X1 e an QVGH'S Dhllr 10x1 e are corrosive creased activity of the catalyst. Preparation of gases and must, H1- large Scale OperatlOnS, be lmetallic salts by the use of nitric and'sulfuric absorbed 01' neutlallzed befOre they Can be disacids necessitates the use of special acid resistposed of finally In most Cases 1f' 15 HQCSSEFY 'C0 4o mg equipment which adds to the cost of pr0 heat the sulphates to 600 C.-900 C. 1n order 95 duction of the catalyst. As the acid products tggorose Teil' These etrenettelpemtufes obtained by the decomposition of these salts are a o e cos o equlpmen an .o e Cost of h. hl o .we there mises the problem of production of the catalyst. These high temperalg y Cor sf th d t hi h. 1 df tures also often materially decrease the activity he @Sposa o ese pro uc s W c mvo ves 1 of many of the catalytic substances and when ac 10o cultles and expense' t tivated carbon and similar substances are used as For some 'reactions a metallic oxlde catalyst 1S carriers a considerable portion of the carrier is more eiiective than the'metalllc catalyst. In destroyed during the heating case a carbonaceous carrier such as charcoal is An olojoot of this invention is to provide o, mothused, the nitrate method Cannot be eadlly @Utod of preparing metallic and metallic oxide cataploed o? 1a tlalge scale tot 1prepae a metallic lysts which will be free from the disadvantages oxi e ca a yS eCauSe O e re dClng aC 1011 inherent in the processes now commonly used in of the carbon at the temperature of decomposithe industry. l tion of the metallic nitrates. When metallic Another object of this invention is to provide nitrates are decomposed 1n the presence of cara'method of preparing catalysts by depositing metallic compounds on a carrier and reducing the deposited compounds at low temperatures.

Another object of this invention is to provide a method of preparing catalytic material from metallic compounds that are more .easily reduced than those compoundsv heretofore used in the preparation of catalysts.

Still another object of this invention is to provide va method of preparing catalytic material from ammoniacal metallic compounds.

With these and other objects in view which may be incident to our improvements, the invention consists in the method of preparing catalysts to be herein set forth and claimed, with the understanding that the several necessary steps comprising the invention may be accomplished in any Y. order found most suitable for carrying the same into practical eiect, and it is apparent that other compounds and elements may be substituted for those enumerated, and similar formations effected without departing from the spirit of the invention and the scope ofthe appended claims.

Our invention comprises the use of ammoniacal solutions of metallic salts for the impregnation of carriers for supporting catalytic material and the treatment of the impregnated carrier to reduce the ammoniacal-metallic compounds to make them available as catalysts, together with the recovery of ammonia during the treating process.

In order to make our invention more clearly understood, we have shown in the accompanying drawing a diagrammatic showing of means for carrying the same into practical effect without limiting the improvements in their useful applications to the particular arrangement which, for purposes of explanation, has been made the subject of illustration.

In the drawing:

The figure shows a diagrammatical representa- Ltion of an arrangement of apparatus suitable for carrying out our process for preparing catalytic material.

It has long been known that ammoniaforms a series of complex compounds with certain metals, such as, for example, copper, nickel, and cobalt. These compounds are 'easily broken down at a relatively low temperature into ammonia and the metal itself or its oxide. The recovery of the ammonia evolvedq in the decomposition may be accomplished without difliculty by absorbing it in water. Since the met'als which form these complex compounds are among those commonly used as catalysts, the use of their ammoniacal solutions to obtain the desired degree of dispersion in the carrier is a marked improvement over the methods which have been used previously for this purpose. According to our'inven'tion solutions of copper, nickel, zinc, and cobalt may be prepared by dissolving these metals and/or their oxides, in ammonium hydroxide in the presence of air. These solutions can then be used to impregnate charcoal and other inert carriers for catalytic purposes.

The exact structure of the complex compounds of ammonia, and the metals previously mentioned is not of particular importance in the preparation of catalysts by this method and will therefore not be discussed. A large number of such com pounds have, however, been isolated and studied by those skilled in the art. All of these compounds possess the property of being easily decomposed at relatively low temperatures, which is an essential property required in our method of preparing catalysts.

Ammoniacal solutions of copper may be prepared by treating the metal and also its oxides 'with ammonia in the presence of water, air, and carbon dioxide. By this method it is possible to readily secure a much higher concentration of the metal in solution than is obtained without the use of carbon dioxide.

All of the compounds formed by the methods used have the common property of being easily decomposed when heated to relatively low temperatures. In no case is it necessary to heat the material to a temperature higher than 150 C., in order to liberate the NH3, CO2 and H2O, and leave only the metallic oxide. We wish it to be clear, however, that higher temperatures may be employed particularly when the catalyst is desired in the metallic form. The valuable materials used in preparing the solution of the metal, NH3, and CO2, and liberated by heating are very easily recovered for further' use by absorption in water. The solution thus obtained is suitable without further treatment for dissolving more of the catalytic metal. If the metal is desired as a catalyst, instead of its oxide, reduction of the oxide may be effected by any of theusual methods.

As an example, an ammoniacal solution containing 3.4% copper was prepared by allowing ammonium hydroxide to trickle over copper turnings, at the same time passing a current of air through the turnings. One hundred and fty parts of this solution were used to impregnate 25 parts of charcoal by allowing the solution to flow over the charcoal contained in a tower, until the charcoal had absorbed as much of the copper as possible. The impregnated charcoal was heated at 150 C. until all ammonia had been driven oil and was then analyzed for copper. The analysis showed 4.12% copper present in the charcoal in the form of copper oxide.

As an example of the use of carbon dioxide to increase the ease of dissolving; a solution as described above was prepared except that a mixture of carbon dioxide and air was passed through the copper turnings while the ammonium hydroxide was ilowing thereover. vBy this method a solution containing 10.2% copper was obtained. When ammoniacal solutions of copper were prepared without the use of carbon dioxide, it was found that solutions containing more than 3.5% copper tended to decompose on standing, depositing copper oxide. When carbon dioxide was used in preparing the solution, no decomposition was apparent even in solutions containing as much as 10% copper.

Various solutions prepared by the above methods were used to impregnate such inert materials as pumice and kieselguhr with results comparable to those obtained when charcoal was used. Recovery of the ammonia and carbon dioxide evolved in the decomposition of the ammoniacal solution was obtained by absorbing it in water and the solutions thus obtained were used in dissolving additional metals.

Our process of impregnating charcoal with copper and copper oxide may be carried out in an arrangement of apparatus such as is diagrammatically shown in the accompanying drawing.

To start the operation of impregnating inert material with copper, the tank l is filled with a solution of ammonium hydroxide. This solution quite often contains between 5 and 10% ammonia. although the concentration is not important since more ammonia may be added later in the process. Metallic copper in the form of lathe turnings, copper sheets, copper scale, or any other form of copper or copper oxides, in which a considerable additional copper.

surface is exposed to the action of the solution is then placed in the tank and is supported therein onthe perforated screen 2. Air, carbon dioxide, and ammonia are then admitted through the valves 3, 4, and5 respectively and bubbled into the solution in the tank. Copper is dissolved by. the vcombined action of these agents.

When the desiredrconcentration of copper is `obtained, the valves 6 and 7 are opened and the solution is forced through conduit 41 into the tank 8 by means of the pump 9. From the tank 8 the solution containing the dissolved copper flows by gravity through the valve 10 and conduit 42 into the impregnator 11. The latter is provided with suitable means for maintaining a constant level of the impregnating solution therein. Conduit 43 serves as a vent to permit the maintenance of a constant level in the tank 11.

An endless conveyor belt 12`of suitable material is mounted in the inclined impregating tank 11 for continuously removing the impregnated material from the solution. The inert material to be impregnated, as for example, activated carbon, or other porous material flows continousuly to the impregnator through the hopper 13 at the same rate that the impregnated material is removed by the conveyor belt. An adjustable baf-L e plate 14 regulates the depth of the layer of the material being carried from the impregnator.

From the conveyor the impregnated material is discharged through the hopper 15 into the rotary dryer 16'. The latter may be of any desired construction and may be heated either externally or internally to the desired temperature by any suitable heating medium. This dryer serves to drive olf-the ammonia, carbon dioxide, and water vapor from the impregnated material. These evolved gases are drawn from the dryer by the .suction pump 17 through the vapor line 18 into the scrubbing towers 19, 20, and 21. These towers are of a constructional type suitable for absorbing vapors in a liquid, and may be provided with packing material which offers a large surface for increasing the absorption of the gases or vapors. Water is introduced into the last tower 21 and is circulated, countercurrent to the ilow of gases, through the towers 20 and 19 by means of the pumps 22 and 23, and absorbs the gases as it ows over the tower packing. The impregnated material in the dryer 16, from which the ammonia, carbon dioxide, and water have been vevolved is discharged through the discharging device 24 into the container 25. n

The solution of ammonia and carbon dioxide from the absorbing tower 19 is pumped into the storage' tank 26 by the pump 27. By opening valves 28 and` 29 and closing valve 30 the solution may be pumped through conduit 44 directly into tank 1 by means of the pump 31, for dissolving If further concentration is desired, this solution may be pumped into the still 32, by closing valve 29 and opening valves 28 and 30. The solution pumped into the still 32 is heated by steam coil 33 and the dissolved ammonia and carbon dioxide are driven off. By opening valves 34 and 40 these gases may be led through the pipe 36 directly into tank l and absorbed in the solution for dissolving additional copper. If not needed for this purpose they may be led into the tank 37 by closing valve 34 and opening valve 35. The tank 37 is kept `full of Water in which the ammonia and carbon dioxide are absorbed. By this latter procedure a concentrated solution of ammonia and carbon dioxide can be obtained in the tank 37 which may, by opening valve 38, be

forced by the pump 39` into the tank 1 for dissolving additional copper.

By the above method of operation practically all of the ammonia and carbon dioxideusedfor dissolving the copper is recovered for "further use. If additional carbon dioxide is needed it maybe introduced into the system by passing the same into tank 1 through valve 5. When theirotary dryer is heated with products of combustion, the latter may be treated by passing through towers 19, 20 and 21 to obtain carbon dioxide which may be used in the dissolution process. ammonia lost in the recovery system can be compensated for by introducing additional ammonia gas from cylinders into the tank l.

l'f catalysts containing nickel, cobalt, zinc'or other metals capable of forming complex ammoniaA compounds are desired the same can be prepared" by the above outlined method with slight varia- Thus it can be seen that our invention provides4 a novel method of preparing` catalytic material from metals or metallic oxides capable of forming ammino salts with ammonia. Our invention also makes it possibleto impregnate material such as activated carbon with a solution of a salt containing the desired catalyst and reduce `the salt to the desired catalytic form Without impairing the properties of the supporting material.

Although we have shown and described the preferred embodiment of our invention, we wish it to be understood that we do not confine ourselves to the precise details of compounding herein set forth, by Way of illustration, as it is apparent that many changes and variations may be made therein by those skilled in the art, without departing from the spirit of the invention or exceeding the scope-of the appended claims.

We claim:

l. A method'for preparing catalytic material comprising treating finely divided metallic particles with an ammoniacal solutionwhile injecting carbon dioxide into the solution to form metallic ammonia compounds.

2. A method of preparing catalytic material comprising treating metallic copper or copper oxide with an ammoniacal solution, while injecting carbon dioxide into the solution, impregnating porous material with the solution formed, heating the impregnated material to a temperature suflicient'to reduce any metallic compounds to the metallic state but insufficient to disintegrate the porous material.

3. A method of preparing catalytic material comprising treating metallic copper or copper oxide with an ammoniacal solution, while injecting carbon dioxide into the solution, impregnating porous material with the solution formed, heating the impregnated material to a temperature suflicient to decompose the metallic ammoniacal salt formed to the oxide state, but not to the metallic state.

4. A method of preparing catalytic material, comprising treating copper or copper oxide with ammoniacal solutions While injecting carbon dioxide therein to form complex ammonia compounds, impregnating porous material with said compounds, heating said impregnated porous material to decompose the complex ammonia compounds to the oxide state, and 'absorbing any vapors liberated during said decomposing step and heating the absorbents to a temperature sunlcient to drive off said absorbed vapors.

5. A method of preparing catalytic material, comprising treating copper or copper oxide with ammoniacal solutions While injecting carbon dioxide therein to form complex ammonia compounds, impregnating porous material With said compounds, heating said impregnated porous material to decompose the complex ammonia compounds to a metallic state, and absorbing any vapors liberated during said decomposing step and heating the absorbents to a temperature sumcient to drive oi said absorbed vapors.

6. A process of preparing catalytic material comprising dissolving a metal Whose atomic weight is between fty-eight and sixty-six in an ammoniacal solution while injecting carbon dioxide therein and decomposing the compound formed into a metallic oxide.

7. A process for preparing catalytic material comprising dissolving copper or copper oxide in an ammoniacal solution, While injecting carbon dioxide in the solution, and decomposing the arnmoniacal complex formed by heat.

8. A process for preparing catalytic material comprising dissolving nickel in an ammoniacal solution, While injecting carbon dioxide in the solution, and decomposing the ammoniacal complex formed by heat.

9. A process for preparing catalytic material comprising dissolving zinc in an ammoniacal solution, While injecting carbon dioxide in the solution, and decomposing the ammoniacal complex formed by heat.

10. A process of preparing catalytic material comprising dissolving a metal of the group consisting of copper, nickel, cobalt, and zinc or the oxide thereof in an ammoniacal solution while injecting carbon dioxide therein, and decomposing the compound formed into a metallic oxide.

ll. A process of preparing a catalytic material comprising dissolving a metal of the group consisting of copper, nickel, cobalt, and zinc or the oxide thereof in an ammoniacal solution in the presence of at least ve per cent carbon dioxide, and decomposing the ammonia complex by heating.

12. A process of preparing a catalytic material comprising treating nely divided particles of a metal of the group consisting of copper, nickel,

Lacasse cobalt, and zinc or the oxide thereof with an aminoniacal solution While injecting at least live per cent carbon dioxide to formA complex ammonia compounds of the metal, impregnating charcoal with this compound, and decomposing the compound by heat.

13. A process of preparing a stable ammoniacal metal complex which will not decompose on standing comprising treating a metal of the group consisting of copper, nickel, cobalt, and zinc or the oxide thereof with an ammonia compound in the presence of at least ve per cent carbon dioxide.

14. A process of preparing a catalyst which comprises treating a metal from the group consisting of copper, nickel, cobalt, and zinc or the oxide thereof with an ammonia solution in the presence of carbon dioxide to form a complex ammonia compound of the metal, impregnating a porous carrier with this compound, and then decomposing the ammonia complex by heating to a temperature of the order of 150 C.

15. A process of preparing a catalyst wherein at least seven percent of a metal or its oxide is impregnated in a carrier which comprises treating a metal from the group consisting of copper, nickel, cobalt, and zinc or the oxide thereof with an ammonia solution while injecting carbon dioxide therein to form a complex ammonia compound of the metal, impregnating a carrier with this compound; and decomposing the ammonia complex by heating to a temperature of the order of 150 C.

1S. A method of preparing catalytic material comprising treating a metal of the group consistm ing of copper. nickel, cobalt, and zinc or the oxide thereof with an ammoniacal solution in the presence of carbon dioxide to form an ammino-salt solution, impregnating porous material with said solution, and subjecting raid treated material to heat for decomposing the ammino salt, absorbing the gases liberated during the solution formed to form further ammino-salt solutions.

17. A method of preparing catalytic material comprising treating a metal of the group consisting of copper, nickel, cobalt, and zinc or the oxide thereof with an ammoniacal solution in the presence of carbon dioxide to form an ammino-salt solution, impregnating porous material with said solution, and subjecting said treated material to heat rcr decomposing the ammino salt, absorbing the gases liberated during said decomposing process to form a solution, treating the solution to drive ol the absorbed ammonia, and introducing the ammonia evolved into the ammino-salt forming solution. l

NICHOLAS E. OGLESBY. HOWARD V. WRIGHT. 

